Treatment of bituminous material



Patented Mar. 19, 1946 2,396,669

UNITED STATES PATENT OFFICE TREATMENT OF BITUMINOUS MATERIAL Laszlo Auer, South Orange, N. J.

No Drawing. Application October 12, 1942, Serial No. 461,788

Claims. (Cl. 106-274) GENERAL FmLn or INVENTION AND STATEMENT or eral constituents being fusible "and relatively in- Omors soluble in carbon disulphide. The expression y- This robitumen implies that the material when submmous 3 21232 zig g gg z zgtg z gg gfg jected to heat or fire will generate, 'or become agents in order to alter the physical and other 5 transformed into materials resembling bitumens,

Properties and characteristics thereof. The presgifig zgggggzfi i to their physical and :2; g ggg ggg i g g ggfi i flgi g gj g gg A more complete classification otcertain of the February 12, 1940 now Patent 2,298,270 issued bituminous materials is as follows. October 13, 1942. A. Bitumens As is mentioned in my copending application 1. Petroleums above identified and also in others elsewhere re- Non-asphaltic petroleum ferred to herein, I believe bituminous products to Semi-asphaltic petroleum be organic isocolloids, i. e., colloidal systems in Asphaltic petroleum which the dispersed phase and the dispersion me- 2. Native mineral waxes dium are both of the same chemical composition, Ozokerite (ceresine when refined) though present in difierent physical states. Montan wax Although there are many classifications, 3. Native asphalts groups and types of bituminous products, they Pure or fairly pure all have certain characteristics in common and I Associated with mineral matter believe the colloidal system of all of them is sub- 4. Asphaltites ject to modification by the use of certain modi- Gilsonite fying agents identified hereinafter. Glance pitch In general, bituminous products are such ma- Grahamits terials as asphalt and asphalt oils, tar and tar B, Pyrobitumens oils, goudron or petroleum distillation residues, 1. Asphaltic pyrobitumens pitches, etc. Elaterite Certain of the bituminous materials are nat- Wurtzilite ural products. for instance, asphalts, mineral Albertite rubber, and gilsonite (sometimes considered as a Impsonite type of asphalt). On the other hand, other bi- Asphaltic pyrobituminous shales tuminous materials are by-products, notably 2. Non-asphaltic pyrobitumens pitches such as residues of petroleum, coal tar, P t fatty acid distillation (goudrons) and rosin dis- Li nit tillation. Coal tars themselves are bituminous Bituminous coal by-products capable of treatment in accordance A thra it coal with the invention. Lignitic and coal shales All of the bituminous materials comprise hyc, Pyrogenous distillate drocarbons in major proportion, although other 1, Pyrogenous waxe constituents may be present. Petroleum paraflin According to one classification, various of these Peat parafiin materials are grouped together as bitumens and Lignite parafiin others as pyrobitumens. Shale paraffin In this classification the term bitumen is ap- 2, T plied to various substances composed principally 4 Oil-gas t of hydrocarbons and being substantially free Water-gas tar from oxygenated bodies, the materials being Pine t sometimes associated with mineral matter, the Hardwood tar non-mineral constituents being fusible and large- P at t ly soluble in carbon disulphide, yielding water Li mt tar insoluble sulphonation products. shale tar The term pyrobitumen, according to the class- Gas-works-coal tar ification just above, comprehends hydrocarbon Coke-oven-coal tar materials, which may or may not contain oxy- Blast-furnace-coal tar genated bodies, these also sometimes being asso- Producer-gas-coal tar ciated with mineral matter, and the non-min- Bone tar D. Pyrogenous residues 1. Pyrogenous asphalts Residual oils Pressure tars Blown petroleum asphalts Residual asphalts Sludge asphalts Wurtzilite asphalts 2. Pitches Oil-gas-tar pitch Water-gas-tar pitch Wood-tar pitch Peat-tar pitch Lignite-tar pitch Shale-tar pitch Gas-works-coal-tar pitch Coke-oven-coal-tar pitch Blast-'furnace-coal-tar pitch Producer-gas-coal-tar pitch Bone-tar pitch Rosin pitch Fatty acid pitch It will be understood that in the case of pyrobitumens, their bituminous content must first be isolated or separated before treatment in accordance with this invention. More specifically, liquid or fusible bituminous products can be advantageously treated by my process and the presence of unsaturated compounds and acidic ingredients (showing, for instance, iodine and acid numbers) are particularly adaptable to treatment.

Many of the foregoing materials have commercial uses in a number of fields, although many others are commonly considered as waste products. According to the invention, it is possible to so modify the various materials as to improve the characteristics of those now in use, and even to so alter the characteristics of many which have not heretofore been employed commercially, thereby making possible use of such "waste materials for various purposes.

For example, it is possible according to the invention to alter the physical consistency of the materials, for instance, to increase the fusion or melting point and also increase the toughness of asphaltic materials and also of other bituminous products. The nature of certain modifications brought about in accordance with the invention will appear more fully hereinafter from an analysis of examples given.

Being organic isocolloids, I believe that the colloidal system of these various bituminous materials, may be influenced by the employment of modifying agents. Such agents, examples of which are given hereinafter, are preferably thoroughly dispersed in the material being treated and for this purpose, I prefer to employ heat in ranges set out more fully herebelow. However, before considering the various factors of the treatment process itself, reference is here made to the modifying agents contemplated for use in accordance with the invention.

Tm: MODIFYING Acnn'r According to the invention, the modifying agents employed are polar compounds in general, especially acidic polar compounds although certain others are also usable as will further appear. By polar compounds I mean compounds having polarity in the molecule, thus including electrolytes. Example are given below.

Polar compounds are of many diflerentclasses, many of which are defined in my copending application above mentioned, and also in others aseaeee referred to hereinafter. The type of modification secured by various groups of modifying agents and even by individual agents, may be quite different, many agents and groups producing results which are quite distinctive, although as before mentioned, I believe the polar compounds are all capable of influencing the colloidal system of the bituminous products in varione of the respects already mentioned and also in other respects.

According to one general classification of polar compounds, the modifying agents may be grouped as follows:

Metal salts of inorganic acids Metal salts of organic acids Inorganic acids Organic acids Metallo-organic compounds Metal alcoholates Aryl-metal compounds Organic esters of inorganic acids Inorganic salts of organic bases Organic esters Amines also constitute a useful class, particu larly the poly-amines, for instance, diamines.

Many of the compounds falling in certain classes mentioned above are also of the type which I have termed two-radical compounds, i. e., compounds having within the molecule an acidic inorganic residue and an organic residue. By an acidic inorganic residue I mean a residue capable of yielding an inorganic acid upon the addition of oneor more hydrogen atoms, OH groups, or water molecules, or upon the application of heat.

Such two radical type compounds may desirably contain a sulpho-, haloor nitro-group.

Typical examples of certain of the foregoin classifications are given just below:

Metal salts of inorganic acids (Formed by various combinations of the following:)

Cations: Anions:

Ammonium Chloride Lithium Bromide Sodium Iodide Barium Carbonate-Bicarbonate Calcium Sulphate Zinc Bisulphate Iron Sulphite Cobalt Bisulphite Lead Nitrate Manganese Nitrite Copper Borate Phosphate Metal salts of organic acids (Formed by various combinations of the following:)

Cations: Anions:

Ammonium Formate Lithium Acetate Sodium Oxalate Barium Citrate Calcium Sallcylate Zinc Phthalate Iron Maleate Cobalt Naphthol-sulphonates Lead Manganese Copper Salts of organic amines Diphenylamine trichloracetate Diphenylamine hydrochloride Diphenylamine hydrobromide m-Nitroaniline hydrochloride Trichloroaniline hydrochloride Diphenyl amine sulphate Diaminodiphenyl sulphate Aniline sulphate Amino-azo-benzene sulphate 4: 4' diamino-diphenyl sulphide Aniline hydrochloride Inorganic acids Carbonic acid Hydrochloric acid Hydrobromic acid Hydriodic acid Sulphuric acid Sulphurous acid Hydrosulphurous acid Hydrosulphuric acid Thiosulphuric acid Nitric acid Nitrous acid Boric acid Phosphoric acid Hydrocyanic Thiocyanic Chlorsulphonic Organic acids 'Iartaric acid Maleic acid Acetic acid Oxalic acid Salicylic acid Phthalic acid Citric acid Trichloracetic acid Naphthenic acids Metal alcoholates Sodium amylate Two-radical compounds A. Containing nitro-group Nitrobenzene o-Nitrophenol p-Nitrophenol Dinitrobenzene Nitro-chloro-benzene Dinitro-chlorobenzene Dinitroaniline p-Nitro-acetanilide Nitrocresyl carbonate m-Nitroaniline hydrochloride Ethyl thioether of Z-nitrobenzene Ethyl thioether of 2:4 dinitrobenzene Ethyl thioether of nitro-aminobenzene 2:4-dinitrobenzene Nitro-aminobenzene B. Containing sulpho-group Benzene sulphonic acid p-Toluene sulphonic acid 2:5 dichlorobenbene sulphonic acid m-Xylidine sulphonic acid p-Toluidine-m-sulphonic acid Naphthalene 2:6 sulphonic acid Beta-naphthol 1:5 sulphonic acid Beta-naphthol 3:6 :8 sulphonic acid Beta-naphthylamine 326:8 trisulphonic acid 2:1 naphthylamine sulphonic acid 2:6 naphthylamine sulphonic acid 2-phenylamine 8 nasphthol- 6 sulphonic acid Methyl-p-toluene sulphonate Ethyl chlorosulphonate Benzene sulphonyl chloride p-Toluene sulphonyl chloride Naphthalene-l-sulphonyl chloride Dimethyl sulphate Diaminodihydroxy anthraquinone disulphonic acid C. Containing halo-group Organic esters of inorganic acids Triphenyl phosphate Tricresyl phosphate and other alkylphenyl phosphates Nitrocresyl carbonate Ethyl chlorosulphonate Dimethyl sulphate Peroscides Barium peroxide Magnesium peroxide Benzoyl peroxide Amines Benzidine Diphenyl-amine Alpha-naphthyl-amine I have found that certain groups of modifying agents are particularly effective in the treatment of bituminous materials, for instance, organic sulphonic acids, organic sulpho chlorides, amines,

and metal sulphides, sulphites and carbonates.

Hereinafter examples are given of the treaT- ment with modifying agents selected from various of the classes above discussed.

TREATMENT CONDITIONS Although the treatment conditions may be varied in accordance with a number of factors,

such as the particular material being treated, the treating agent selected and the characteristics desired, in general, the treatment conditions should conform with the following.

With respect to temperature, it is first noted that while some modification may be brought about merely by dispersing the modifying agent in the bituminous material at normal room temperature, in general, the treatment temperature should be above about 200 C., but not above the point at which appreciable destructive distillation or decomposition occurs, or not above the flash point of the material. Usually it is found, for instance with asphalts, pitches and the like, that temperatures between about 200 C. and about 320 C. are effective.

The quantity of modifying agent employed will also depend somewhat on the material being treated, on the modifying agent selected, and on the particular characteristics desired. For various purposes a fairly wide range is usable, for instance, from an appreciable trace, such as .1% or .5% up to about 10%. Ordinarily not more than about 5% is required, and many of the modifying agents are effective in the neighbor hood of about 1%.

The duration of the heating will similarly depend n the materials used and the results desired. Usually the heating should be continued at least until thorough dispersion of the treating agent is obtained. Ordinarily it is found that treatment for a period of at least 30 minutes is required and frequently for several hours, for instance up to or hours.

In general, increase in temperature or duration of heating, and sometimes also in percentage of modifying agent, tends to promote the reaction and/or produce a more extensive modification.

The nature of the atmosphere in contact with the reaction mass will influence the modification which occurs. The reaction may be carried out either in the presence or in the absence of air, depending upon the results desired, although frequently no special precaution need be taken in this regard and the treatment may be carried out in an open vessel. Variation in pressure, either above or below atmospheric pressure, may also influence the reaction in some cases.

In situations where it is desired to exclude air,

- this may be accomplished by employing vacuum or by introducing some suitable gas into the reaction vessel to serve as a blanket on the surface of the batch. Gases suitable for this purpose are nitrogen, CO2, S02, HzS, amongst others. Certain of these gases (S02 and Has) may also be bubbled through the reaction mass, in which event secondary reaction may take place.

Various combinations of modifying agents above mentioned, as well as disclosed in my copending applications herein identified, may be employed for special purposes, and in addition, the modifying agent may be produced in situ, by introducing materials which will react under the conditions of the treatment to produce the modifying agent desired.

Light treatment and wave treatment of various types also influence the reaction, for instance, treatment with visible light, ultra violet light or with electrical potential differences. Irradiation with oscillating energy of various wave lengths, X-rays, etc., may also be used.

Treatment of the modified bituminous materials with sulphur may be employed to advan; tage, in order to secure sulphurized products.

Certain of the materials, for instance, asphaltic materials, are also advantageously vulcanized,

EXAMPLES A series of comparative experiments were conducted in order to indicate modifications secured from a. number of different modifying agents which are typical of groups. In this series an asphalt mixture was treated (Barber Asphalt Company material identified as G460, the material being suitable for use in making battery boxes).

The experiments of Table I were carried out in 1 a one liter open container, the charge being 300 grams. No mechanical agitation was employed though hand stirring was adopted to initially distributethe modifying agent throughout the asphalt.

All of the experiments were heated and maintained at the treatment temperature for fl ve hours, the treatment temperature being different with different experiments,

Various different modifying agents were employed in different percentages, as will appear from the foregoing table. The results of this comparative series are indicated in Table No. I v

just below.

In this series some oxidation-may have occurred, in view of the small size of the batches, and because the heating was carried out in open containers. This oxidation may be in part responsible for the increase in melting points,

All temperatures are given in degrees centigrade.

Table No. I

Percent Size of Agent batch Temp.

Degree: Gram Benzidine base do .do do i p Toluene -sulphocb1oride.

p-Toluene-sulphonic acid.

. Sodium bisulphite do (Asphalt without any treatment). (Heated withoutagent).

A second series in the same containers and under the same reaction conditions, except for the following changes:

(1) 800 gram batches were used, except where the batch had to be reduced to 500 grams on account of foaming during the reaction.

(2) The containers, instead of being open, were covered, and

(3) CO: blanket was used.

Table No. II

in OM11} Ex. Per- 5 Size o! Agent cent Temp. (balmind batch method) Degrees Drama Grams 13...- Benzidine base-.. l 300 137 800 14-.-- --d 6 300 137.5 800 15.... p-ggluene-suiphoehio- .5 300 105 800 e. 16--.- .do 2 300 91% 500 17...- do 5 300 144 500 18.... p-Totl luene-sulphonic .5 300 98 800 ac 19...- -d0 2 300 104 500 20..-- ----.d0 5 300 126 500 21---- Sodium bisulphite- 5 300 119 800 22. do 1 300 113 800 1A.--. (Asphalt without any 119.5 trea ment 0--.. (Heatedwithoutagent). 300 99 800 From the above tables several effects of the modifying treatment will at once be apparent.

surprising to note that exceptionally small quantitles of sulphur and very short vulcanizing periods, yield extensive changes when the materials have been previously treated with modifying agents according to the present invention.

Example No. 34

300 gms. Goudron tar: vacuum a plied The pasty mass melts on heating and troths vigorously. In a short time thickening begins and in 65 minutes from starting it comes on temperature (230-240 C.) and in two hours a sample is taken. It is then reheated for a further hour and after sampling is poured out yielding a soft, black. elastic solid.

Example No. 35

500911. Goudron 5% sodium bisl ll phite (to start) I In this the object was to obtain a hard, stiff, solid which melted between 50 and 130 C.

The conditions of experiment are best followed extent of modification. by the followin tabular summary:

Times Temp. Notes Product (1. 0 26 Start-froths on heating Thick viscous oil.

Rfore, stopped to clean side tube.

Mixture frothing badly and some irothings in side tube dist. flask, there- 130 estart 254 Bad frothlng fig Erotlging-stopped heating and a sample poured into a tin Stifl black solid (sample 1). es 4% hours 290 Stopped and shut down for night 0n restarting 28 Restart 284 Slight froth. 5%; hours 2G2 Slight froth-stopped heating and a sample poured into a tin Stifl black solid softer than sample 1 (sample 2). 5% hours 230 Restart 5 hours, minutes.-. 290 Stopped and a further 2% modifying agent added (making total percent to 7 hours 290 Bad irothing which had occurred again has now gradually subsided 7 hours, 40 minutes... 294 Stopped for a sample Hard stifl solid (sample 3). 7 hours, minutes.-. 200 Restart 8 hours, 45 minutes... 272 Stopped and final product poured ofl Brittle black solid.

No distillation occurred during the experiment. Product becomes plastic at 52 C. and melts to viscous liquid at 120 0. Original becomes plastic at 40 C. and melts to viscous liquid at 100 0. Moreover, it will be noted that in general the Example 36 modification results in a raising of the softening 300 gms. Goudron tar: point of the material. The softening point of 6% magnesium peroxidJ applied blank B should be particularly noted and compared with the numbered examples.

Some of the products of the examples in Tables I and II were aftertreated with sulphur to further increase their melting point and toughness. The results are shown in Table III below.

The mixture was heated in vacuum, the pressure varying between 20 and 24 inches mercury. The mixture reached 284 C. after 35 minutes heating, when a slight froth was present and some distillation began. After being kept at 290-304 C. for 1 hour, the product had gone Table No. III solid. The solidification took place gradually during that period. The heating was continued Fx Mmmab Sm v l V! gotten-t S. I for a further A hour, when the product began 3 gellteolfr pm" 3 f; i g 63 to char and the heating was therefore stopped.

- Piroduct.-Black rather brittle solid.

N. B.: 23" Per o 220 Mim 187 "75 (1) To remove the product from the flask 2 g g :83 it wasnecessary to break the flask, as the 1 235 10 125 150 product failed to melt even at 320 C. g-- g 322 g 15 g (2) A small piece of the product, placed in a 29111 2 280 15 137 150 I tin lid and heated over a Bunsen flame, g $8 3 1 3 did, however, finally melt. 32:: j 3 250 28 142 150 (3) A sample of the above was heated in a 2 15 134 test tube with a thermometer inside. The

\ following observations being taken:

Mass becomes plastic at 90 C.

Mass becomes a thick viscous liquid at 1 Ball and ring method.

Whereas sulphur treatment (vulcanization) of bituminous products is known in the art, it is Example 37 the melting point of the gouclron. When cooled down to room temperature, the mass displayed considerable elasticity as compared with the starting material, and in addition, had a higher melting point than the starting material. When mixed with fillers in hot condition, the mass dis played great binding iorce.

Various of the foregoing and other variations in treatment may be employed, as is mentioned in my copending application above identified. Such supplemental matters need not be considered in detail herein, since reference may be made for that purpose to said copending applications, and also to certain other prior applications mentioned herebelow, all of which discloses certain features in common with the present application-to wit, Serial No. 359,425 (now Patent No. 2,213,944); Serial No. 446.172 (now Patent 2,213,943); Serial No. 446,170 (now Patent No. 2,234,949); and Serial No. 143,786 (now Patent No. 2,189,772).

Some of the modifying agents may act as dissolution promoting agents, as described in various of my prior applications and also in my issued Patent No. 2,293,038.

I claim:

.1. A process for modifying the properties of bituminous materials, which process comprises incorporation in the bituminous material of more than 1% and up to 10% of an o'rganic compound which is a member of the class consisting of benzidine, diphenylamlne and alpha-naphthylamine, and heating the mixture at a temperature which is at least 250 C. and is below the decomposition or distillation point of the major portion of the material undergoing treatment for at least half an hour.

2. A process in accordance with claim 1 in which the bituminous material is an asphaltic material.

3. A process in accordance with claim 1 in which the bituminous material is asphalt.

4. A process in accordance with claim 1 in which the bituminous material is a fatty acid,

pitch.

5. A process in accordance with claim 1 in which the bituminous material is a pitch.

6. A process in accordance with claim 1 in which the treated material is subsequently vulcanized.

7. A process in accordance. with claim 1 in which the organic compound is benzidine.

8. A modified asphaltic material having dispersed therein more than 1% and up to about 10% of an organic compound which is a member of the class consisting of benzidine, diphen ylamine and alpha-naphthylamine, said material having increased fusion point, as compared with the same material unmodified, said increased fusion point being obtained by the aid of heating to at least 250 C. for at least half an hour.

9. A process in accordance with claim 1 in which the organic compound is diphenylamine.

10. A process in accordance with claim 1 in which the organic compound is alpha-naphthylamine.

LASZLO AUER. 

